Professional Documents
Culture Documents
First Law Thermodynamics
First Law Thermodynamics
Thermodynamic variables describe the state of the thermal system, and the
ideal gas law relates these variables. We can very usefully describe the state as a
point on a two-dimensional plot, such as a p-V diagram, a p-T diagram, or a V-T
diagram. Changes, or transformations in the state of a thermal system can be rep-
resented as curves on such diagrams - at least if thermal equilibrium is established
at every stage of the transformation. A change in which thermal equilibrium is
maintained throughout, such as the sufficiently slow compression of a piston in an
insulated cycling is called a reversible process. Conversely, a gas expanding
1
Reversible process Is one where thermodynamic equilibrium is maintained through-
out, such as the sufficiently slow compression of a piston in an insulated
cylinder.
1. Heat Flow
1. Heat flow is a transfer of energy.
2. Thermal systems have internal energy related to the system’s thermal prop-
erties.
Heat transfer can happen via diffusion, thermal conduction or radiation, for
an open system it can occur through absorption of water vapor (latent heat). For
many applications, heat transfer is secondary to processes introduced through mo-
tion, which operate on timescales of order one day and shorter (particularly in the
boundary layer) In the free atmosphere and away from clouds, the prevailing form
of heat transfer is radiative. Operating on a timescale of order weeks. If no heat
is exchanged between a system and its environment, the process is adiabatic, and
diabatic otherwise. Adiabatic approximation is a good approx. in many cases be-
cause heat transfer is slow compared to motion.
The connection between heat flow and temperature change is the heat capac-
ity, C (which is always positive). A small heat flow dQ into a system will change
the temperature by a small amount dT with proportionality constant C:
dQ = CdT (1)
The value of the heat capacity depends on the material and is proportional to
the mass. We can define the specific heat c as the heat capacity per unit mass
(dq = cdT ).
Note: If we decrease (increase) the heat flow from a substance with a large
specific heat capacity, such as water, the temperature of the substance will fall
(rise) only slightly. This is why large bodies of water have strong moderating
effects on the climate in their vicinity.
2
1a. Heat flow depends on the path
While heat capacity is defined in terms of temperature change, the conditions for
temperature change are not unique. The proportionality constants between heat
absorption and temperature change define the 1) specific heat capacity at constant
pressure:
dqp
cp = (2)
dT
and the 2) heat capacity at constant volume:
dqv
cv = (3)
dT
where the subscript denotes isobaric and isochoric processes respectively.
3
Figure 1: Phase Change of water
4
2. Work done by Thermal Systems
If we restrict our analysis to a system comprised of a gas, and consider only work
done by or on the gas by expansion or compression. The example of the cylinder
of fixed cross-sectional area with a fitted movable frictionless piston (Fig 3.4).
The pressure-volume thermodynamic diagram of the states of the system is also
shown. As the piston moves outward an infinitesimal distance dx the work done
while its pressure remains essentially constant at p is:
dW = F dx (5)
= pAdx
= pdV
dw = pdα (7)
If we think of the work done by a thermal system as the area under a curve of
p vs V , the fact that work done depends on the path of the change becomes evident.
3. Internal Energy
In thermal (internal) energy is associated with the energy of the molecules of a
thermal system. Changes in internal energy, are not path dependent. This con-
5
trasts sharply with work or heat flow which are path dependent. So we can write:
Z B
dU = UB − UA (8)
A
We can’t actually do this with work or heat flow because we need to know the
path. We will not change the mathematical notation of dW or dQ, but keep in
mind these are not true differentials. Internal energy is purely a function of state.
dQ = dU + dW (9)
It is more useful to express this equations in terms of specific properties (divide
by mass) z = Z/m where Z is an extensive property that depends on the mass m
of the system, and z is an intensive property that doesn’t depend on the mass.
dq = du + dw (10)
This is the mathematical formulation of the First Law of Thermodynamics and
embodies three related ideas:
dq = du + pdα (11)
note:
6
• The work performed by the system and the heat transferred into it is path
dependent
We can introduce the state variable enthalpy:
h ≡ u + pα (12)
dh = dq + αdp (14)
dq = du + pdα (15)
For an isochoric process this reduces to:
dqv ∂u
= = cv (16)
dT ∂T α
This means that the heat capacity at constant volume measures the rate of
internal energy change with temperature during and isochoric process.
7
In a similar fashion we can use enthalpy expressed as h = h(T ):
dq = dh − αdp (17)
For an isobaric process this reduces to:
dqp ∂h
= = cp (18)
dT ∂T p
This means that the heat capacity at constant pressure measures the rate of
enthalpy increase with temperature during and isobaric process. Over ranges of
pressure and temperature relevant to the atmosphere, the specific heats may be
regarded as constants for an ideal gas. The change of internal energy during an
isochoric process is proportional to the change of temperature alone, and similarly
for the change of enthalpy during an isobaric process.
u = cv T (19)
h = cp T (20)
We can express the first law in terms of specific heat and using the ideal gas
law d(pα) = RdT
h−u pα
cp − cv = = =R (21)
T T
3 5
For a monoatomic gas cv = 2
R, for a diatomic gas cp = 2
R, since air is
mainly diatomic.
Specific heats for dry air:
• cp = 1004.5JK −1 kg −1
• cv = 717.5JK −1 kg −1
8
And we define the dimensionless constants
dq = cv dT + pdα (24)
dq = cp dT − αdp (25)
dqv = cv dT (26)
dqp = cp dT (27)
0 = cv dT + pdα (28)
0 = cp dT − αdp (29)
0 = cv d ln T + Rd ln α (30)
0 = cp d ln T − Rd ln p (31)
0 = cv d ln p + cp d ln α (32)
9
the change of a second state variable. Adiabatic system possesses only one inde-
pendent state variable and only one thermodynamic degree of freedom.
10
4d. Potential Temperature
Potential temperature θ is defined as the temperature assumed by the system when
compressed or expanded adiabatically to a reference pressure of p0 = 1000mb.
Using Poisson’s equation 35, an adiabatic process from state (p, T ) to the refer-
ence state (p0 , θ) is
θp−κ
0 = Tp
−κ
(36)
So the potential temperature is described by
κ
p0
θ=T (37)
p
Theta is a state varaible and invariant along an adiabatic path in state space.
Adiabatic behavior is a good approximation for many atmospheric applications
because over a fairly large scale of motions, the timescale for an air parcel to ad-
just to changes of pressure ant to perform expansion work is short compared to
the characteristic timescale of heat transfer.
ii. Skew T-log p Diagram One way to display these changes is on a Skew T -
ln p chart. On this chart, dry adiabats are slightly curved lines that run from the
lower right to the upper left with an angle between isotherms and dry adiabats of
approx 90◦ . This diagram was developed by the US Air Force in 1952
cp dT = αdp (38)
dT α 1
= = (39)
dp cp ρcp
11
Figure 3: Rogers and Yau, 1.4
Since
dT dT dp 1 g
= =− ρg = − = −Γ (40)
dz dp dz ρcp cp
Γ = 9.8◦ Ckm−1 is the dry adiabatic lapse rate. This shows that as the air
parcel ascends (descends) dry adiabatically, its temperature decreases (increases)
at the fixed rate of nearly 10◦ C per km.
12
Figure 4: Pielke Blog
13